JP5361883B2 - Hydrophilic coating agent, hydrophilic coating, and hydrophilic substrate - Google Patents

Abstract

Disclosed is a hydrophilic coating film having high hardness and excellent abrasion resistance. The hydrophilic coating film also has excellent solvent resistance and alkali resistance. Also disclosed is a hydrophilic coating agent containing (A) a colloidal silica sol, (B) an acrylic polymer containing an active hydrogen and having a weight average molecular weight (Mw) of 5,000-200,000, (C) a silane coupling agent, (D) a polylactone polyol and (E) a curing agent. The hydrophilic coating agent contains less than 30% by mass of (F) a surfactant containing an active hydrogen relative to the total mass of the component (E) and the component (F). The mass ratio between the component (A) and the component (B), namely (A)/(B) is from 5/95 to 95/5; the mass ratio between the total of the component (A) and the component (B) and the component (C), namely (A + B)/(C) is from 30/70 to 95/5; and the mass ratio between the component (B) and the component (D), namely (C)/(D) is from 90/10 to 10/90.

Description

  The present invention relates to a hydrophilic coating for imparting antifogging properties to spectacle lenses, window materials, etc., a hydrophilic coating obtained from the hydrophilic coating, and a hydrophilic substrate on which the hydrophilic coating is formed. .

  Conventionally, hydrophilic coating agents for imparting antifogging properties to spectacle lenses, window materials and the like, which are made of glass or plastic material as a base material, are known.

  For example, Patent Document 1 below discloses a hydrophilic hard coat composition for forming a hydrophilic coating film that achieves both scratch resistance and antifogging properties. Specifically, a monomer having at least three (meth) acryloyl groups in one molecule, a hydrophilic monomer having a functional group selected from a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and an inorganic colloid sol A hydrophilic hard coat composition is disclosed.

  Further, Patent Document 2 below discloses a coating agent for forming an antifogging film having excellent wear resistance and capable of reducing the time of the leveling step. Specifically, it comprises a mixture of a water-absorbing polyol such as organic isocyanate and polyethylene glycol, an acrylic polyol having a hydroxyl group-containing monomer such as 2-hydroxyethyl methacrylate as a structural unit, an active hydrogen group-containing surfactant, and a solvent. A coating agent is disclosed.

  Patent Document 3 below discloses an antifogging spectacle lens in which an antifogging coat layer made of an organic material and an inorganic material is formed on a plastic lens substrate for spectacles on which a hard coat layer is formed. As a specific example of the anti-fogging coating layer, a coating composition containing colloidal silica, polyvinyl alcohol, polyacrylic acid and a water-containing organic solvent is laminated as a first layer, and methyl silicate is formed on the first layer. A layer formed by laminating a second layer containing aluminum acetylacetone and a water-containing organic solvent is disclosed. Further, as a specific example of the anti-fogging coating layer, a coating composition containing ethyl silicate, colloidal silica, and a water-containing organic solvent is laminated as a first layer, and a polyvinyl alcohol partial kenne is laminated on the first layer. A layer formed by laminating a second layer containing a compound, methyl silicate, acetylacetone aluminum, epoxy silica and the like is disclosed.

  Moreover, the following patent document 4 discloses an antifogging coating material for forming a coating film having an excellent antifogging performance life. Specifically, an anti-fogging paint containing colloidal silica sol and a hydrophilic polymer as essential components is described. Specific examples of the hydrophilic polymer include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, modified polyvinyl pyrrolidone, and hydrophilic acrylic polymer. Further, it is described that the anti-fogging paint may further contain a crosslinking agent such as a polyisocyanate compound.

  Patent Document 5 below discloses a technique for providing a coating agent excellent in adhesion between glass and a coating layer, and glass excellent in scratch resistance and scattering prevention performance using the same. And it is described that this coating agent contains a silane coupling agent, polycaprolactone, polydimethylsiloxane, and an isocyanate resin or a melamine resin.

The hydrophilic film formed from the coating agent disclosed in any of the above documents does not have all of hydrophilicity, high hardness, scratch resistance, solvent resistance, and alkali resistance.
JP 2005-187576 A JP 2006-169440 A Japanese Patent Laid-Open No. 2005-234066 JP 2005-314495 A JP 2006-290696 A

  An object of the present invention is to provide a hydrophilic film having high hardness and excellent scratch resistance, and further having excellent solvent resistance and alkali resistance.

One aspect of the present invention includes (A) a colloidal silica sol, (B) an acrylic polymer having a weight average molecular weight (Mw) of 5,000 to 200,000 having active hydrogen, (C) a silane coupling agent, and (D) poly A hydrophilic coating agent containing a main component containing a lactone polyol, (F) a surfactant having active hydrogen, and (E) a curing agent, and the mass of component (A) and component (B) The ratio [(A) / (B)] is 5/95 to 95/5, and the mass ratio of the sum of the components (A) and (B) and the component (C) [(A + B) / (C )] Is 30/70 to 95/5, the mass ratio [(B) / (D)] of component (B) to component (D) is 90/10 to 10/90, and (F) activity 0 to 30 wt% based on the total weight of the content of the surfactant component (B) and component (F) with hydrogen, it hydrophilic coating characterized by It is.

Another aspect of the present invention includes (A) a colloidal silica sol, (B) an acrylic polymer having an active hydrogen-containing weight average molecular weight (Mw) of 5,000 to 200,000, (C) a silane coupling agent, (D) A hydrophilic coating agent containing a polylactone polyol, (F) a surfactant having active hydrogen, and (E) a curing agent, in the nonvolatile component of the main agent, the content ratio of the colloidal silica sol (a) is 5 to 60 wt%, the 10 to 60 mass% content ratio of the acrylic polymer (B), the content of the silane coupling agent (C) is 5 Hydrophilic content in which the content ratio of the (D) polylactone polyol is 5 to 75 mass% and the content ratio of the surfactant (F) having active hydrogen is 0 to 15 mass%. Coating The

  Another aspect of the present invention is a hydrophilic film obtained by applying any one of the above hydrophilic coating agents to a substrate and curing it.

  Another aspect of the present invention is a hydrophilic base material characterized by being coated with the above hydrophilic film.

  Objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description.

  Preferred embodiments of the invention are described in detail below. In addition, this invention is not limited at all by embodiment described below.

The hydrophilic coating agent in the present embodiment includes (A) a colloidal silica sol, (B) an acrylic polymer having an active hydrogen-containing weight average molecular weight (M _w ) of 5,000 to 200,000, (C) a silane coupling agent, A hydrophilic coating containing (D) a polylactone polyol, (F) a surfactant having active hydrogen, and (E) a curing agent, (A) component and (B) The mass ratio [(A) / (B)] to the component is 5/95 to 95/5, and the mass ratio of the sum of the components (A) and (B) to the component (C) [(A + B ) / (C)] is 30/70 to 95/5, and the mass ratio [(B) / (D)] of the component (B) to the component (D) is 90/10 to 10/90, (F) The surfactant having active hydrogen is 0 to 30% by mass based on the total amount of the component (B) and the component (F).

  The colloidal silica sol (A) is a component that imparts hydrophilicity to the resulting coating by a silanol group (—Si—OH) on the surface, and further imparts high hardness and solvent resistance.

  The colloidal silica sol (A) is a colloid or sol of a silica-based compound having a silanol group (—Si—OH) having water, methanol, ethanol, isopropyl alcohol, butanol, xylene, dimethylformamide or the like as a dispersion medium. Examples of the colloidal silica sol include those containing silica fine particles and long-chain molecules as dispersoids, which are produced using a basic catalyst using methyl silicate, ethyl silicate and oligomers thereof as raw materials.

  The average particle size of the dispersoid is preferably 1 to 200 nm, and more preferably 10 to 100 nm, from the viewpoint of excellent stability of the coating material and transparency after curing. The average particle diameter is a value calculated in terms of specific surface area.

  The content (solid content) of the silica-based compound in the colloidal silica sol (A) is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass from the viewpoint of excellent particle stability.

  Specific examples of colloidal silica sol (A) include commercially available products such as MEK-ST and methanol silica sol Snowtex series (both manufactured by Nissan Chemical Co., Ltd.); Quartron (manufactured by Fuso Chemical Co., Ltd.); Cataloid S ( Catalyst Chemical Industry Co., Ltd.); Ludox (Grace Co., Ltd.); Silica Doll (Nihon Chemical Industry Co., Ltd.); Adelite (Asahi Denka Kogyo Co., Ltd.) and the like.

  The content ratio of the colloidal silica sol (A) in the nonvolatile component of the main component of the hydrophilic coating agent of this embodiment is 5 to 60% by mass, more preferably 5 to 55% by mass, and particularly preferably 10 to 30% by mass. . When the content ratio of the colloidal silica sol (A) is less than 5% by mass, the hydrophilicity and solvent resistance of the resulting film tend to be lowered, and the hardness tends to be lowered. On the other hand, when the content of the colloidal silica sol (A) exceeds 60% by mass, the hardness of the resulting coating becomes too high, so that cracks are likely to occur and the scratch resistance tends to decrease. is there.

  The acrylic polymer (B) in the present embodiment is a component that forms a hydrophilic film while maintaining alkali resistance, solvent resistance, and the like on the resulting film.

  The acrylic polymer (B) in the present embodiment is an acrylic polymer having active hydrogen and a weight average molecular weight of 5,000 to 200,000. Due to the active hydrogen contained in the acrylic polymer (B), the acrylic polymer (B) forms a crosslinked structure with the colloidal silica sol (A) via the silane coupling agent (C). Moreover, the active hydrogen of the acrylic polymer (B) also becomes a crosslinking point by the curing agent (E).

  The acrylic polymer (B) having active hydrogen can be obtained by polymerizing a monomer mixed solution containing a radical polymerizable monomer having a functional group having active hydrogen (hereinafter also simply referred to as active hydrogen-containing monomer). Specific examples of the polymerization method include solution polymerization, suspension polymerization, emulsion polymerization and the like. Among these, it is preferable to use solution polymerization in which a monomer mixed solution is dissolved in a solvent and polymerized in the presence of a polymerization initiator as necessary.

  Specific examples of the functional group having active hydrogen include a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, an amide group, a phosphate group, and a mercapto group. Among these, a hydroxyl group is preferable from the viewpoint of excellent reactivity with the coupling agent and excellent stability of the coating agent.

  The acrylic polymer (B) is not particularly limited as long as it is a polymer containing an active hydrogen-containing monomer unit as a constituent unit, and is a radical polymerization having no active hydrogen copolymerizable with the active hydrogen-containing monomer and the active hydrogen-containing monomer. It may be a copolymer with a reactive monomer (hereinafter also simply referred to as an active hydrogen-free monomer) or a homopolymer of an active hydrogen-containing monomer.

  The content ratio of the active hydrogen-containing monomer unit in the acrylic polymer (B) is preferably 10% by mass or more, more preferably 20% by mass or more, and 100% by mass or less, and further preferably 80% by mass or less. When the content ratio of the active hydrogen-containing monomer unit is too low, the hydrophilicity of the resulting film tends to be insufficient.

The weight average molecular weight (M _w ) of the acrylic polymer (B) is in the range of 5,000 to 200,000, preferably 10,000 to 100,000, and more preferably 10,000 to 30,000. When the weight average molecular weight is less than 5,000, the water resistance and alkali resistance of the surface of the formed hydrophilic film are lowered. On the other hand, when the weight average molecular weight exceeds 200,000, the compatibility with the (A) colloidal silica sol is reduced, so that agglomeration occurs in the coating agent, making it difficult to apply or a good coating film is formed. It can no longer be obtained.

  Moreover, as a hydroxyl value of an acrylic polymer (B), it is preferable that it is 10-70, Furthermore, it is 15-65. If the hydroxyl value is too low, the hydrophilicity tends to decrease. Moreover, when the said hydroxyl value is too high, there exists a tendency for the coating film obtained to become cloudy or the colloidal silica sol in a coating agent to aggregate. The hydroxyl value is a value measured by potentiometric titration in accordance with JIS-K0070.

  In the hydrophilic coating agent of the present embodiment, the mass ratio [(A) / (B)] between the colloidal silica sol (A) and the acrylic polymer (B) is 5/95 to 95/5 (0.05 to 19). 20/80 to 80/20 (0.25 to 4), more preferably 25/75 to 75/25 (0.3 to 3), and particularly preferably 25/75 to 40/60. (0.3 to 0.6). When A / B is less than 5/95, the solvent resistance decreases. On the other hand, when A / B is higher than 95/5, a good coating film cannot be obtained due to cracks and the like, and the alkali resistance and scratch resistance are lowered.

  The content ratio of the acrylic polymer (B) in the nonvolatile component of the main component of the hydrophilic coating agent of the present embodiment is preferably in the range of 10 to 60% by mass, more preferably 20 to 55% by mass, particularly preferably. Is 30-45 mass%. When the content ratio of the acrylic polymer (B) is less than 10% by mass, the hydrophilicity of the resulting film is lowered and the alkali resistance tends to be lowered. On the other hand, when the content ratio of the acrylic polymer (B) exceeds 60% by mass, the hardness of the resulting coating film tends to decrease, the solvent resistance decreases, and the scratch resistance tends to decrease. .

  Examples of the radical polymerizable monomer having a hydroxyl group include a hydroxyl group-containing (meth) acrylic acid ester, vinyl ether, or (meth) acrylic acid ester glycol-based adduct.

  Specific examples of the radical polymerizable monomer having a hydroxyl group include, for example, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Esters; hydroxyalkyl vinyl ethers such as 4-hydroxybutyl vinyl ether and cyclohexanedimethanol monovinyl ether; hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether and cyclohexanedimethanol monoallyl ether; polyalkylenes such as polyethylene glycol, polypropylene glycol, and tetramethylene glycol Polyol mono (meth) acrylate, an ester of polyol and (meth) acrylic acid; a plastic manufactured by Daicel Chemical Industries, Ltd. Cell F series manufactured polycaprolactone oligomer radical reactive unsaturated double bond and the macromonomer introduced a hydroxyl group; and polyol mono (meth) acrylate or a polyalkylene polyol and an adduct of ε- caprolactone.

As specific examples of polyol mono (meth) acrylate, commercially available products such as Blemmer AET series, APT series, AE series, AEP series, Blemmer AP-400, AP-550, AP-800, Blemmer PEP series, PET series , PPT series, PP series (all manufactured by NOF Corporation); MA series manufactured by Nippon Emulsifier Co., Ltd .; New Frontier NF series manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; Among these, polyol mono (meth) acrylate is preferable because it does not gel during polymerization and does not rapidly increase in viscosity, and enables stable polymerization control. In addition, a macromonomer in which a radical-reactive unsaturated double bond and a hydroxyl group are introduced into a polycaprolactone oligomer is particularly preferable from the viewpoint of improving scratch resistance.

  Specific examples of the radical polymerizable monomer containing a carboxyl group include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, ω -Unsaturated carboxylic acids such as carboxy-polycaprolactone mono (meth) acrylate.

  Specific examples of the radically polymerizable monomer containing a sulfonic acid group include, for example, vinyl sulfonic acid, vinyl benzene sulfonic acid, allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and the like.

  Specific examples of the radical polymerizable monomer containing an amide group include, for example, (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, isopropyl (meth) acrylamide, dimethylaminopropyl acrylamide, diacetone acrylamide, N -Methylolacrylamide etc. are mentioned.

  Specific examples of the radical polymerizable monomer containing an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate and the like.

  Specific examples of the radical polymerizable monomer containing a phosphate group include (meth) acryloyloxyalkyl acid phosphates such as 2- (meth) acryloyloxyethyl acid phosphate.

  On the other hand, specific examples of the radical polymerizable monomer having no functional group having active hydrogen include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meta ) Acrylate, benzyl (meth) acrylate, alkyl (meth) acrylate such as dicyclopentadienyl (meth) acrylate; glycidyl (meth) acrylate; trifluoroethyl (meth) acrylate; polysiloxane-containing (meth) acrylate; styrene, Aromatic vinyl compounds such as vinyltoluene and α-methylstyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; alkoxysilyl group-containing vinyl compounds such as 3-methacryloxypropyltriethoxysilane and vinyltrimethoxysilane; And so on.

  These monomers may be used alone or in combination of two or more.

  Specific examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t-hexyl peroxyneodecanate, and t-butyl peroxybivalate. -Azo compounds such as azobis-iso-butyronitrile, 2,2-azobis-2,4-dimethylvaleronitrile, 2,2-azobis-4-methoxy-2,4-dimethylvaleronitrile. The polymerization initiators may be used alone or in combination of two or more. The blending ratio of the polymerization initiator is preferably 0.01 to 8 parts by mass, and more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer.

  Examples of the solvent used in the solution polymerization include ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester organic solvents such as methyl acetate, ethyl acetate, and butyl acetate, dimethylformamide, dimethyl sulfoxide, and N-methyl-2- Polar solvents such as pyrrolidone, alcoholic organic solvents such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, aromatic hydrocarbon organic solvents such as toluene, xylene, “Sorvesso 100” (manufactured by Exxon Chemical), n-hexane, cyclohexane Aliphatic hydrocarbon / alicyclic hydrocarbon organic solvents such as methylcyclohexane, “Loose”, “Mineral Spirit EC” (both manufactured by Shell), cellosolve organic solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, Te Examples thereof include ether organic solvents such as trahydrofuran and dioxane, and carbitol organic solvents such as n-butyl carbitol and iso-amyl carbitol. These may be used alone or in combination of two or more.

  The acrylic polymer (B) is blended in a liquid state such as an acrylic resin solution, an acrylic emulsion, and an acrylic suspension. The solid content concentration of the acrylic polymer (B) in the acrylic resin solution, acrylic emulsion, or acrylic suspension is 10 to 80% by mass, more preferably 20 to 60% by mass when the acrylic polymer is produced. It is preferable from the viewpoint of workability.

  On the other hand, the silane coupling agent (C) in this embodiment is used to form a crosslinked structure between the colloidal silica sol (A) and the acrylic polymer (B) or polylactone polyol (D). That is, the silane coupling agent (C) reacts with the active hydrogen of the acrylic polymer (B) or polylactone polyol (D) through the functional group at one end, while reacting with the alkoxysilyl group at the other end. A silanol group and a silanol bond on the surface of (A) are formed. Then, by forming a crosslinked structure between the colloidal silica sol (A) and the acrylic polymer (B) or the polylactone polyol (D), hydrophilicity and high alkali resistance are imparted to the obtained coating surface.

  Specific examples of the silane coupling agent (C) include glycidoxypropyltrimethoxysilane (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd., Silaplane S-510 manufactured by Chisso Co., Ltd.), glycidoxy, and the like. Epoxy group-containing silane coupling agents such as propyltriethoxysilane (KBE403 manufactured by Shin-Etsu Chemical Co., Ltd., Z-6041 manufactured by Toray Dow Corning Co., Ltd.); aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) ) KBM903, Toray Dow Corning Co., Ltd. Z-6610, etc.), aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd. KBE903, Chisso Co., Ltd. Silaplane S330, etc.), etc. Group-containing silane coupling agent; mercaptopropyltrimethoxysilane (KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., Toray Dowco) Mercapto group-containing silane coupling agents such as Z-6062 manufactured by Ning Co., Ltd .; Ureidopropyltriethoxysilane (KBE585 manufactured by Shin-Etsu Chemical Co., Ltd.), Z-6676 manufactured by Toray Dow Corning Co., Ltd. ) And the like; and isocyanate group-containing silane coupling agents such as isocyanatepropyltriethoxysilane (KBE9007 manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Among these, glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, and isocyanatepropyltriethoxysilane are preferable from the viewpoint of excellent stability and reactivity of the coating agent.

As a compounding ratio of the silane coupling agent (C), a mass ratio of the total amount (A + B) of the colloidal silica sol (A) and the acrylic polymer (B) to the silane coupling agent (C) [(A + B) / (C )], 30/70 to 95/5 (0.42 to 19), preferably 50/50 to 90/10 (1 to 9), and more preferably 60/40 to 85/15 (1. 5 to 5.6), particularly preferably 70/30 to 80/20 (2.3 to 4). When the mass ratio [(A + B) / (C)] is less than 30/70, the film formability is lowered, so that the surface hardness, water resistance, and the like are lowered. The mass ratio when the [(A + B) / ( C)] is more than 95/5, by cross-linking point between the colloidal silica sol (A) and the acrylic polymer (B) is reduced, colloidal silica sol (A) Since the bond at the interface between the polymer and the acrylic polymer (B) is reduced, the hydrophilicity and alkali resistance are reduced.

  The content ratio of the silane coupling agent (C) in the nonvolatile component of the main component of the hydrophilic coating agent of the present embodiment is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass. When the content of the silane coupling agent (C) is less than 5% by mass, a crosslinked structure is not sufficiently formed between the colloidal silica sol (A) and the acrylic polymer (B) or the polylactone polyol (D). Tend to be.

  The polylactone polyol (D) in the present embodiment crosslinks with the colloidal silica sol (A) via the silane coupling agent (C), and also crosslinks with the curing agent (E). Gives elasticity. This imparts scratch resistance to the resulting coating.

  The polylactone polyol (D) is obtained, for example, by ring-opening polymerization of a lactone monomer using a polyhydric alcohol as an initiator.

  Specific examples of the polyhydric alcohol include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, and 2-methyl 1,3-propane. Diol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentane Diol, 2-ethyl 1,3-hexanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, glycerin, trimethylolpropane, tri Examples include polyols such as methylol octane and pentaerythritol.

  Examples of the lactone monomer include ε-caprolactone, α-methyl-ε-caprolactone, β-methyl-ε-caprolactone, γ-methyl-ε-caprolactone, β, δ-dimethyl-ε-caprolactone, 3, 3, 5 -Caprolactones such as trimethyl-ε-caprolactone; polyvalerolactones such as δ-valerolactone and β-methyl-δ-valerolactone; propiolactones; butyrolactones; enanthlactones; dodecanolactone, etc. or derivatives thereof Etc.

  For example, polycaprolactone diol is represented by the following general formula (1).

  Polycaprolactone triol is a trivalent hydrocarbon group R ′ in which three polyester chains having terminal hydroxyl groups as shown in the following formula (2) are bonded.

  Specific examples of the polylactone polyol (D) include commercially available products such as polycaprolactone triol (for example, Plaxel 303, 305, 308, 312 manufactured by Daicel Chemical Industries, Ltd.), polycaprolactone diol (manufactured by Daicel Chemical Industries, Plaxel). 205, 208, 210, 212). As the polylactone polyol (D), a polycaprolactone polyol having excellent rebound resilience due to a relatively large number of carbon atoms connecting the polyester bonds is particularly preferable.

  As a blending ratio of the polylactone polyol (D), the mass ratio [(B) / (D)] of the acrylic polymer (B) and the polylactone polyol (D) is 90/10 to 10/90 (0.11 to 0.11). 9), preferably 80/20 to 40/60 (0.6 to 4). When the mass ratio [(B) / (D)] is less than 10/90, high scratch resistance can be obtained, but hydrophilicity decreases due to a decrease in the proportion of the acrylic polymer (B). On the other hand, when the mass ratio [(B) / (D)] exceeds 90/10, sufficient scratch resistance cannot be obtained.

  The content ratio of the polylactone polyol (D) in the non-volatile component of the main component of the hydrophilic coating agent of the present embodiment is in the range of 5 to 75% by mass, further 10 to 50% by mass, and particularly 15 to 30% by mass. It is preferable that When the content of the polylactone polyol (D) is less than 5% by mass, the scratch resistance tends to decrease. On the other hand, when the content of the polylactone polyol (D) exceeds 75% by mass, the hydrophilicity tends to decrease.

  In the coating agent of this embodiment, you may mix | blend small amount of surfactant (F) which has active hydrogen. When a small amount of the surfactant (F) having active hydrogen is blended, the hydrophilicity of the resulting coating surface is further improved. Further, since the surfactant has active hydrogen, the hydrophilicity improving effect is maintained for a long time by reacting with the silane coupling agent (C) or the curing agent (E). However, when the blending ratio is too large, hardness and water resistance are lowered. Therefore, the content ratio is limited to the range described later.

  The surfactant (F) is not particularly limited as long as it has active hydrogen. Specific examples include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant having a functional group having active hydrogen. Examples of the functional group having active hydrogen include a hydroxyl group, a carboxyl group, an amino group, and an amide group.

  Specific examples of the anionic surfactant containing active hydrogen include, for example, castor oil monosulfate, castor oil monophosphate, sorbitan fatty acid ester sulfate, sorbitan fatty acid ester phosphate, polyoxyalkylene glycerol ether monosulfate, polyoxyalkylene glycerol Ether monophosphate, perfluoroalkyl ester phosphate and the like can be mentioned.

  Specific examples of the cationic surfactant containing active hydrogen include dialkanolamine salts, polyoxyalkylene alkylamine ether salts, polyoxyalkylene alkyl ammonium salts, polyoxyalkylene dialkanol amine ether salts, and the like.

  Examples of the nonionic surfactant containing active hydrogen include polyoxyethylene polyoxypropylene block polymers, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, and polyglycerin fatty acid esters.

  Specific examples of the amphoteric surfactant containing active hydrogen include N, N-di (β-hydroxyalkyl) N-hydroxyethyl-N-carboxyalkylammonium betaine, N, N-di (polyoxyethylene) -N -Alkyl-N-sulfoalkylammonium betaine, perfluoroalkyl betaine, etc. are mentioned.

  When the surfactant (F) is contained, the content ratio is 30% by mass or less with respect to the total amount [(B) + (F)] of the acrylic polymer (B) and the surfactant (F), Preferably, it is 20% by mass or less, preferably 0% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more. When the blending ratio of the surfactant (F) exceeds 30% by mass, the hardness, water resistance, alkali resistance, and solvent resistance of the resulting coating are lowered.

  The content ratio of the surfactant (F) in the nonvolatile component of the main component of the hydrophilic coating agent of this embodiment is preferably in the range of 0 to 15% by mass, and more preferably 1 to 5% by mass. When the blending ratio of the surfactant (F) is too high, the hardness, water resistance, alkali resistance, and solvent resistance of the resulting film tend to be lowered.

  On the other hand, the curing agent (E) in the present embodiment imparts high alkali resistance, water resistance, solvent resistance, etc. to the formed film by crosslinking the acrylic polymer (B) and the polylactone polyol (D). It is a component that

  The curing agent (E) is not particularly limited as long as it is a compound having at least two functional groups having reactivity with the active hydrogen of the acrylic polymer (B) and the polylactone polyol (D).

  Specific examples of the curing agent (E) include at least two or more reactive functional groups, such as polyisocyanate, melamine resin curing agent, epoxy curing agent, carbodiimide curing agent, oxazoline curing agent, and the like. Is mentioned. Among these, polyisocyanates and melamine resin-based curing agents are particularly preferable because polyisocyanates are excellent in reactivity even at relatively low temperatures.

  Specific examples of the polyisocyanate include trifunctional polyisocyanates having biuret, isocyanurate, and allophanate structures starting from hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, and the like. Examples of commercially available products are modified with hydrophilic groups such as D-165N (biuret structure), D-170N (isocyanurate structure), D-178N (allophanate structure), and ethylene oxide manufactured by Mitsui Takeda Chemical Co., Ltd. WD series made by Mitsui Takeda Chemical Co., Ltd., which is a water-dispersed polyisocyanate, Duranate WB40-100 made by Asahi Kasei Chemicals Co., Ltd. Series etc. are mentioned.

  In addition, specific examples of the melamine resin-based curing agent include, for example, a Nicalac series manufactured by Sanwa Chemical Co., Ltd. as a commercial product.

  Specific examples of the epoxy-based curing agent include, for example, an epicoat series manufactured by Yuka Shell Epoxy Co., Ltd. and an epolite series manufactured by Kyoeisha Chemical Co., Ltd. as commercially available products.

  Further, specific examples of the carbodiimide curing agent include, for example, a carbodilite series manufactured by Nisshinbo Co., Ltd. as a commercial product.

  In addition, specific examples of the oxazoline-based curing agent include, for example, Epochros series manufactured by Nippon Shokubai Co., Ltd. as a commercial product.

  The blending ratio of the curing agent (E) is appropriately selected depending on the types of the acrylic polymer (B) and the polylactone polyol (D), the active hydrogen content, and the like. Specifically, for example, when the acrylic polymer (B) is a hydroxyl group-containing acrylic polymer and the curing agent (E) is a polyisocyanate, the isocyanate of the polyisocyanate with respect to 1 equivalent of the hydroxyl group of the hydroxyl group-containing acrylic polymer. The blending ratio is preferably such that the group is 0.2 to 3 equivalents. Further, for example, when the polylactone polyol (D) is a polylactone triol and the curing agent (E) is a polyisocyanate, the isocyanate group of the polyisocyanate is 0. 1 with respect to 1 equivalent of the hydroxyl group of the polylactone triol. The blending ratio is preferably 2 to 3 equivalents. In addition, as the total amount of the curing agent (E), the total amount required for curing the acrylic polymer (B) and the polylactone polyol (D) is blended.

  As a content rate of the hardening | curing agent (E) of this embodiment, it is 10-200 mass parts with respect to 100 mass parts of main agents, Furthermore, 20-100 mass parts, Especially, it is the range of 30-60 mass parts. It is preferable. When the content ratio of the curing agent (E) is too low, the curing reaction does not proceed sufficiently, so that film formation tends to be difficult. On the other hand, when the content rate of the said hardening | curing agent (E) is too high, there exists a tendency for hydrophilicity to fall.

  The surface hydrophilic coating agent of this embodiment may further contain a cured metal catalyst (G). By blending the cured metal catalyst (G), the hardness and alkali resistance of the coating obtained by promoting the condensation reaction between the colloidal silica sol (A) and the silane coupling agent (C) can be further improved.

  Specific examples of the cured metal catalyst (G) include tin, titanium, zinc, iron, cobalt, aluminum metal salts, alkoxides, and chelate compounds. Specific examples include aluminum monoacetylacetonate, di-isopropoxytitanium bis (ethylacetoacetate), zirconium tetraethylacetoacetate and the like.

  As a content rate of the hardening metal catalyst (G) in the non-volatile component of the main component of the hydrophilic coating agent of this embodiment, 0.01-0.2 mass%, Furthermore, 0.05-0.1 mass% It is preferable that it is the range of these. When the blending ratio of the cured metal catalyst (G) is too high, the hardness and alkali resistance of the resulting coating are improved, but the hydrophilicity tends to decrease.

  In the surface hydrophilic coating agent of the present embodiment, an ultraviolet absorber, an antioxidant, a light stabilizer, a heat stabilizer, an antistatic agent, an antifoaming agent, etc., as necessary, as long as the effects of the present invention are not impaired. These various additives may be further blended. On the other hand, it is preferable that the surface hydrophilic coating agent of this embodiment does not contain polydimethylsiloxane. Polydimethylsiloxane is known as a component that improves scratch resistance. However, polydimethylsiloxane is hydrophobic. Therefore, hydrophilicity is lost when polydimethylsiloxane is contained in a large amount. Therefore, even if it does not contain polydimethylsiloxane or contains it, it is preferable to suppress it to a ratio of about 0.2% by mass or less and further about 0.1% by mass or less in the main agent.

The main component of the surface hydrophilic coating agent of the present embodiment is used as necessary, colloidal silica sol (A), acrylic polymer (B) solution, silane coupling agent (C), polylactone polyol (D), and It is prepared by mixing the surfactant (F) having active hydrogen, the cured metal catalyst (G), other additives and the like so as to have the above-described blending ratio. In addition, it is preferable that a hardening | curing agent (E) is mixed with a main ingredient just before application | coating. Specifically, for example, a colloidal silica sol (A), a silane coupling agent (C), a polylactone polyol (D), a surfactant (F) blended as necessary, and a cured metal catalyst (G) are reserved. After mixing, the main agent is obtained by mixing while gradually adding the solution of the acrylic polymer (B). And a surface hydrophilic coating agent is prepared by adding a hardening | curing agent (E) to a main ingredient just before apply | coating to a base material. More specifically, for example, colloidal silica sol (A), a silane coupling agent (C), polylactone polyol (D), surfactant to be blended as necessary (F), and curing the metal catalyst (G ) In a container and heated to 40 ° C. Then, the acrylic polymer (B) is gradually dropped into the container over a period of about 30 to 60 minutes. And after completion | finish of dripping, a main ingredient is adjusted by further stirring for about 30 to 60 minutes at 40 degreeC. And just before apply | coating to a base material, a surface coating agent is prepared by mix | blending and mixing a hardening | curing agent (E) with a main ingredient.

  The prepared surface hydrophilic coating agent is preferably applied to the substrate before the reaction proceeds excessively.

  The base material is not particularly limited, and various resin base materials such as polycarbonate resin, polyacrylic resin, styrene resin, various metal base materials such as stainless steel, steel, and aluminum, and inorganic base materials such as glass are used without particular limitation. It is done. Further, the form of the substrate is not particularly limited, such as a plate, a film or a molded product.

  The coating method is not particularly limited, and various coating methods such as dipping, roll coating, spin coating, and bar coating can be used without particular limitation.

  The applied surface coating agent is thermally cured by heating at a temperature of about 60 to 180 ° C., preferably about 80 to 150 ° C. for 15 to 120 minutes, preferably about 30 to 60 minutes. Thereby, a hydrophilic film is formed. Moreover, as long as it is possible, hardening by normal temperature hardening or photocuring may be sufficient.

  Although the film thickness of a hydrophilic film is not specifically limited, For example, it is preferable that it is about 2-90 micrometers, and also about 5-50 micrometers.

  Such a surface coating agent is preferably used for forming a hydrophilic coating on lenses such as glasses and goggles, window materials for architecture, vehicles, and instruments, electronic device parts, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the following "%" and "part" mean a mass standard.

  The present invention is not limited to the following examples, and can be arbitrarily modified within the scope of the technical idea of the present invention.

<< Synthesis example of acrylic polymer having hydroxyl group >>
(Synthesis Example 1)
In a reaction vessel, 233 parts of methyl ethyl ketone (MEK) was charged as a solvent, and the temperature was raised to 60 ° C.

  On the other hand, a monomer component consisting of 50 parts of methyl methacrylate (MMA) and 50 parts of polyethylene glycol monomethacrylate (MA-50A, manufactured by Nippon Emulsifier Co., Ltd.) was added to azobis-2-methylbromonitrile (ABN-) as a polymerization catalyst. E and 4.0 parts of Nippon Hydrazine Kogyo Co., Ltd.) were mixed by stirring to prepare a monomer mixture.

The monomer mixture was added dropwise to the above mixed solvent at 60 ° C. over 3 hours, and the reaction was terminated after 3 hours. Thus, a resin solution containing an acrylic polymer having a hydroxyl value of 25 and a weight average molecular weight (M _w ) of 28000 was produced.

(Synthesis Example 2)
Similar to Synthesis Example 1, except that 100 parts of monomer composed of MA-50A is used as the monomer component and 1 part of 2-mercaptomethanol is blended as the chain transfer agent, the hydroxyl value is 55, and the weight average molecular weight (M _w ). A resin solution containing 8000 acrylic polymers was prepared.

(Synthesis Example 3)
In the same manner as in Synthesis Example 1, except that a monomer component consisting of 50 parts of MMA, 30 parts of N, N-dimethylacrylamide (DMAA), and 20 parts of 2-hydroxyethyl acrylate (2-HEA) was used as the monomer component. A resin solution containing an acrylic polymer having a hydroxyl value of 31 and an amide group and a weight average molecular weight (M _w ) of 14,000 was produced.

(Synthesis Example 4)
An acrylic polymer having a hydroxyl value of 15 and a weight average molecular weight (M _w ) of 26000 was obtained in the same manner as in Synthesis Example 1 except that a monomer component consisting of 85 parts of MMA and 15 parts of MA-50A was used as the monomer component. A resin solution containing was prepared.

(Synthesis Example 5)
As monomer components, 50 parts of MMA, and 50 parts of a macromonomer (Placcel FM5, manufactured by Daicel Chemical Industries, Ltd.) in which an unsaturated double bond having radical polymerizability and a primary hydroxyl group are introduced into the polycaprolactone oligomer one by one. A resin solution containing an acrylic polymer having a hydroxyl value of 65 and a weight average molecular weight (M _w ) of 30000 was produced in the same manner as in Synthesis Example 1 except that a monomer comprising:

(Synthesis Example 6)
A hydroxyl value of 55 was obtained in the same manner as in Synthesis Example 1 except that 100 parts of a monomer composed of MA-50A was used as the monomer component, 6 parts of ABN-E was used as the polymerization catalyst, and 2 parts of 2-mercaptomethanol was added. Thus, a resin solution containing an acrylic polymer having a weight average molecular weight (M _w ) of 4000 was produced.

(Synthesis Example 7)
Acrylic polymer having a hydroxyl value of 25 and a weight average molecular weight (M _w ) of 250,000 is contained in the same manner as in Synthesis Example 1 except that the addition amount of the polymerization catalyst (ABN-E) is changed from 4 parts to 0.5 parts. A resin solution was prepared.

In Table 1, the kind of polymerization composition in the synthesis examples 1-7, the weight average molecular weight ( _Mw ) of the obtained acrylic polymer, the viscosity and non-volatile content of a resin solution, and the hydroxyl value of an acrylic polymer are shown collectively.

"Example"
The hydrophilic coating agent was manufactured as follows using the acrylic polymer obtained by the synthesis examples 1-7.

The other raw materials used in this example will be described collectively below.
(A) Colloidal silica sol MEK-ST (manufactured by Nissan Chemical Co., Ltd., Snowtech series): dispersed particle size 10-15 nm, non-volatile content 30%
(C) Silane coupling agent / S-510 solution: MEK solution of glycidoxypropyltrimethoxysilane (Silaplane S-510, manufactured by Chisso Corporation), nonvolatile content 30%
-KBE-9007 solution: MEK solution of isocyanate propyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.), nonvolatile content 30%
(D) Polylactone polyol / Placcel 303 solution: MEK solution of polycaprolactone triol (Placcel 303 solution, manufactured by Daicel Chemical Industries, Ltd.), nonvolatile content 30%
(E) Curing agent-WB40-100 solution: MEK solution of Duranate WB40-100 (hydrophilic group-added modified hexamethylene diisocyanate (HDI) burette type water-dispersed polyurethane resin manufactured by Asahi Kasei Chemicals Corporation), nonvolatile content 30%
D-165N solution: MEK solution of Takenate D-165N (hexamethylene diisocyanate (HDI) burette type polyretane resin manufactured by Mitsui Takeda Chemicals Co., Ltd.), nonvolatile content 30%
・
D-170N solution: MEK solution of Takenate D-170N (hexamethylene diisocyanate (HDI) nurate type polyretane resin manufactured by Mitsui Takeda Chemicals Co., Ltd.), nonvolatile content 30%
・
D-178N solution: MEK solution of Takenate D-178N (hexamethylene diisocyanate (HDI) allophanate-type polyretane resin manufactured by Mitsui Takeda Chemicals Co., Ltd.), nonvolatile content 30%
(F) Surfactant / Evan U105 solution: MEK solution of polyoxyethylene polyoxypropylene glycol ether (Evan U105 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), nonvolatile content 30%
(G) Curing catalyst / TN-12 solution: MEK solution of dibutyltin laurate (TN-12 manufactured by Sakai Chemical Industry Co., Ltd.), nonvolatile content 30%

Example 1
With the composition as shown in Table 2, a hydrophilic coating agent was prepared by the following method.

  First, 20 parts of MEK-ST, 20 parts of S-510 solution, and 20 parts of Plaxel 303 solution were charged in a reaction vessel and heated to 40 ° C.

  Next, 40 parts of the acrylic polymer solution obtained in Synthesis Example 1 was dropped into the reaction vessel over 45 minutes, and after completion of the dropwise addition, the base material was prepared by stirring at 40 ° C. for 30 minutes.

  And the hydrophilic coating agent was obtained by stirring and mixing 53 parts of WB40-100 solutions as a hardening | curing agent with the obtained main ingredient.

(Examples 2 to 14)
A hydrophilic coating agent was obtained in the same manner as in Example 1 except that it was prepared according to the composition shown in Table 2.

(Comparative Examples 1-10)
A hydrophilic coating agent was obtained in the same manner as in Example 1 except that it was prepared according to the composition shown in Table 3.

  The various obtained hydrophilic coating agents were evaluated according to the following evaluation methods.

<< Evaluation method of hydrophilic coating agent >>
A curing agent (E) was blended with the main agent obtained in Examples 1 to 14 and Comparative Examples 1 to 10, and mixed with stirring to prepare a hydrophilic coating agent. And after apply | coating the obtained coating agent to the glass plate of 150 mm x 70 mm x 0.5 mm (thickness) with the applicator 4mil, it dried on 120 degreeC and the conditions for 20 minutes, and produced the test plate. At this time, a film having a thickness of about 15 μm was obtained. And it used for the following evaluation test using the obtained test board.

  However, the hydrophilic coating obtained in Comparative Example 10 could not be tested because the coating solution was agglomerated.

(Appearance evaluation)
In accordance with the test method of 4.4 “Appearance of coating film” of JIS K 5600-1-1, the transparency and the presence or absence of cracks were determined according to the following criteria.
Excellent: colorless and transparent, no cracks.
Inferior: White turbidity or crack occurred.

(Pencil hardness)
A pencil hardness test was performed in accordance with the test method of JIS K 5600-5-4 “Scratch hardness (pencil method)”. In the pencil hardness test, B, HB, F, and H are arranged in order from the lower hardness to the higher hardness. Also, the greater the number that precedes “H”, the higher the hardness, and the greater the number that precedes “B”, the lower the hardness.

(Adhesion)
An adhesion test was carried out in accordance with the test method of “Cross cut method” of JIS K 5600-5-6. Specifically, 100 crosscuts (cut pieces) were formed by cutting the coating film applied to the test plate in the vertical and horizontal directions with a cutter knife and reaching the substrate. Then, a cellophane adhesive tape (for example, product number Nichiban Tape No. 1 manufactured by Nichiban Co., Ltd.) was pasted on the cross cut. And after peeling the cellophane adhesive tape affixed, the number of crosscuts which remained without peeling was counted.

(Antistatic test)
In accordance with the test method of JISK-6911, the surface resistance value [Ω] on the surface of the test plate was measured using a digital high resistance meter (Hiresta UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation). In addition, it shows that antistatic property is so high that the multiplier of surface resistance [Ω] is small.
Excellent: Multiplier of surface resistance value [Ω] is 10 ¹² or more Inferior: Multiplier of surface resistance value [Ω] is 10 ¹³ or more

(Anti-fouling test; evaluation of wiping off oily soil components)
0.1 g of normal hexadecane was dropped on the surface of the test plate. Then, normal hexadecane adhering to the test plate surface was wiped 10 times with a cellulose nonwoven fabric (Pencot M-3: manufactured by Asahi Kasei Corporation) under a load of 300 g. Using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.), haze (turbidity) on the surface of the test plate before and after the test was measured. Then, ΔE was calculated. The smaller the value of ΔE, the better the wiping property of oily dirt, that is, the better the antifouling property.
Excellent: ΔE is 0-1
Normal: ΔE is 1-3
Inferior: ΔE is 3 or more

(water resistant)
The test plate was immersed in water at 23 ° C. ± 2 ° C. for 3 days. Then, the appearance of the test piece after immersion was observed, and the water resistance was determined according to the test method of 4.4 “Appearance of coating film” of JIS K 5600-1-1.
Excellent: colorless and transparent.
Normal: Translucent Inferior: Whitening or dissolution.

(Alkali resistance)
The test plate was immersed in a 5% aqueous sodium hydroxide solution at 23 ° C. ± 2 ° C. for 3 days. Then, the appearance of the test piece after immersion was observed, and alkali resistance was determined according to the test method of 4.4 “Appearance of coating film” of JIS K 5600-1-1.
Excellent: colorless and transparent.
Normal: Translucent Inferior: Whitening or dissolution.

(Solvent resistance)
Acetone was dropped onto the surface of the coating formed on the test plate surface, and then a rubbing test was performed 50 times with a load of 100 g. Then, the solvent resistance was judged according to the test method of 4.4 “Appearance of coating film” of JIS K 5600-1-1.
Excellent: Clearly colorless and transparent.
Normal: Translucent Inferior: Whitening or dissolution.

(Abrasion resistance)
On the surface of the test plate, steel wool (Bonster Sales Co., Ltd., product number # 0000) was reciprocated 50 times in the horizontal direction while applying a load of 300 g per 1 cm ² . The number of scratches generated at that time was visually observed.
Excellent: The number of scratches was 0-2.
Normal: The number of scratches was 2-4.
Inferior: The number of scratches was 5 or more.

(Anti-fogging property)
The coated surface of the test plate was opposed to the surface of hot water at 50 ° C. with a spacing of 1 cm, and the time until the coating surface began to cloud was measured.
Excellent: It took more than 2 minutes to start cloudy.
Normal: The time until cloudy began was 1 minute or more and less than 2 minutes.
Inferior: Time until cloudy start was less than 1 minute.

(Surface hydrophilicity (water contact angle))
A 0.4 μL water droplet was dropped on the surface of the test plate, and the contact angle was measured with a contact angle meter (Kyowa Interface Science Co., Ltd., Drop Master500).

  The results are shown in Tables 2 and 3.

  All the coatings obtained from the surface coating agents prepared in Examples 1 to 14 had a water contact angle of 50 ° or less, and were excellent in hydrophilicity. Further, the pencil hardness was H or more. Furthermore, it was excellent in scratch resistance. Further, the appearance was colorless and transparent, and no cracks were generated. Furthermore, the solvent resistance, alkali resistance, water resistance, antifogging property, antistatic property and antifouling property were also excellent.

On the other hand, the hydrophilic film obtained in Comparative Example 1 had low scratch resistance. This is because (D) polylactone polyol is not contained. Moreover, the hydrophilic film obtained in Comparative Example 2 also had low scratch resistance. This is because the content ratio of (D) polylactone polyol was too low. Moreover, the hydrophilic film obtained in Comparative Example 3 had low hydrophilicity. This is because the content ratio of the acrylic polymer (B) was too low. Further, the hydrophilic film obtained in Comparative Example 4 was cracked, and the alkali resistance, scratch resistance, etc. were low. This is compared with the content of the colloidal silica sol (A), because the content of the acrylic polymer (B) was too low. Moreover, the hydrophilic film obtained in Comparative Example 5 had low solvent resistance. This is compared with the content of the acrylic polymer (B), because the content of the colloidal silica sol (A) was too low. Moreover, the hydrophilic film obtained in Comparative Example 6 had low alkali resistance and relatively low hydrophilicity. This is compared with the content of the colloidal silica sol (A) and the acrylic polymer (B), because the content of the silane coupling agent (C) was too low. The hydrophilic film obtained in Comparative Example 7 had low hardness, low adhesion, low water resistance, alkali resistance, etc., and low hydrophilicity. This is compared with the content of the colloidal silica sol (A) and the acrylic polymer (B), because the content of the silane coupling agent (C) is too high. Moreover, the hydrophilic film obtained in Comparative Example 8 had low hardness, low adhesion, low water resistance, alkali resistance, and the like. This is because the content ratio of the surfactant (F) having active hydrogen was too high. Moreover, the hydrophilic film obtained in Comparative Example 9 had low water resistance and alkali resistance. This is because the molecular weight of the acrylic polymer (B) was too low. Moreover, the hydrophilic coating film obtained in Comparative Example 10 was unable to form a practical coating film due to aggregation of the coating solution. This is because the molecular weight of the acrylic polymer (B) is too high, and the (A) colloidal silica sol becomes difficult to disperse.

As described above in detail, the hydrophilic coating agent of one aspect of the present invention includes (A) a colloidal silica sol, (B) an acrylic polymer having an active hydrogen and a weight average molecular weight (M _w ) of 5,000 to 200,000, (C) A silane coupling agent, (D) a polylactone polyol, and (E) a curing agent, and (F) a surfactant having active hydrogen as a sum of components (B) and (F). The mass ratio [(A) / (B)] of the component (A) and the component (B) is 5/95 to 95/5 without containing more than 30% by mass with respect to the amount, (A) The mass ratio [(A + B) / (C)] of the sum of the component and the component (B) to the component (C) is 30/70 to 95/5, and the ratio of the component (B) to the component (D) The mass ratio [(B) / (D)] is 90/10 to 10/90. According to such a hydrophilic coating agent, it is possible to form a hydrophilic film having high hardness, excellent scratch resistance, and excellent solvent resistance and alkali resistance.

  Moreover, when the hydroxyl value of the said acrylic polymer (B) is 10-70, it is preferable from the point which can provide more superior hydrophilicity to a film.

  In addition, it is preferable that the curing agent (E) contains at least one selected from the group consisting of a nurate polyurethane resin, a burette polyurethane resin, and an allophanate polyurethane resin. From the viewpoint of sex.

  Further, the hydrophilic coating agent further contains a cured metal catalyst (G), and the condensation reaction between the colloidal silica sol (A) and the silane coupling agent (C) is promoted. It is preferable from the viewpoint that the hardness and alkali resistance can be further improved.

The hydrophilic coating agent according to another aspect of the present invention includes (A) a colloidal silica sol, (B) an acrylic polymer having an active hydrogen-containing weight average molecular weight (Mw) of 5,000 to 200,000, and (C) silane. A hydrophilic coating agent containing a coupling agent, (D) a polylactone polyol, (F) a surfactant having active hydrogen, and (E) a curing agent. in the non-volatile components, the content of 5 to 60% by weight of colloidal silica sol (a), is preferably from 10 to 30 mass%, the content of 10 to 60 wt% of an acrylic polymer (B), preferably 30 to 45% by mass, the content of the silane coupling agent (C) is 5 to 30% by mass, preferably 10 to 20% by mass, and the content of the (D) polylactone polyol is 5 to 75%. The content ratio of the surfactant having (F) active hydrogen is 0 to 15% by mass, preferably 15 to 30% by mass. According to such a hydrophilic coating agent, it is possible to form a hydrophilic film having high hardness, excellent scratch resistance, and excellent solvent resistance and alkali resistance.

  Moreover, mass ratio [(A) / (B)] of (A) component and (B) component is 5 / 95-95 / 5, and the sum total of (A) component and (B) component, and (C) The mass ratio [(A + B) / (C)] to the component is 30/70 to 95/5, and the mass ratio [(B) / (D)] of the (B) component to the (D) component is It is preferable that it is 90/10-10/90.

  Moreover, the hydrophilic coating film of another one aspect | mode of this invention is obtained by apply | coating one of the said hydrophilic coating agents to a base material, and making it harden | cure. Such a hydrophilic film has high hardness, excellent scratch resistance, and excellent solvent resistance and alkali resistance.

  Moreover, the hydrophilic base material of the other one aspect | mode of this invention was coat | covered with the said hydrophilic film. Such a hydrophilic substrate has a high hardness, excellent scratch resistance, and a surface excellent in solvent resistance and alkali resistance.

  The hydrophilic coating agent of the present invention is widely used for hydrophilic hard coat materials, antifogging coating agents, antistatic coating agents, antifouling coating agents such as oil stains and fingerprints, and the like.

Claims (14)

(A) colloidal silica sol;
(B) an acrylic polymer having an active hydrogen and a weight average molecular weight (Mw) of 5,000 to 200,000;
(C) a silane coupling agent having a functional group that binds to the component (B ) at one end and an alkoxysilyl group that binds to the component (A) at the other end ;
(D) a polylactone polyol;
(F) a main agent containing a surfactant having active hydrogen;
(E) a curing agent, and a hydrophilic coating agent,
The mass ratio [(A) / (B)] of the component (A) and the component (B) is 5/95 to 95/5,
The mass ratio [(A + B) / (C)] of the sum of the component (A) and the component (B) and the component (C) is 70/30 to 80/20 ,
The mass ratio [(B) / (D)] of the component (B) and the component (D) is 90/10 to 10/90,
(F) Ri 0 to 30% by mass relative to the total weight of the content of the surfactant having an active hydrogen component (B) and component (F),
Hydrophilic coating agent content of the component (C) in the non-volatile components of the main agent, Ru 10-20% by mass, and wherein the.   The hydrophilic coating agent according to claim 1, wherein the acrylic polymer (B) has a hydroxyl value of 10 to 70.   The hydrophilic coating agent according to claim 1 or 2, wherein the curing agent (E) contains at least one selected from the group consisting of a nurate polyurethane resin, a burette polyurethane resin, and an allophanate polyurethane resin.   The hydrophilic coating agent according to any one of claims 1 to 3, further comprising a cured metal catalyst (G). (A) colloidal silica sol;
(B) an acrylic polymer having an active hydrogen and a weight average molecular weight (Mw) of 5,000 to 200,000;
(C) a silane coupling agent having a functional group that binds to the component (B ) at one end and an alkoxysilyl group that binds to the component (A) at the other end ;
(D) a polylactone polyol;
(F) a main agent containing a surfactant having active hydrogen;
(E) a curing agent, and a hydrophilic coating agent,
In the nonvolatile component of the main agent,
The content of the colloidal silica sol (A) is 5 to 60% by mass,
The content ratio of the acrylic polymer (B) is 10 to 60% by mass,
The content ratio of the silane coupling agent (C) is 10 to 20% by mass ,
The content ratio of the polylactone polyol (D) is 5 to 75% by mass,
Ri content 0 to 15% by mass of the surfactant (F) having an active hydrogen,
Mass ratio of the colloidal silica sol (A) and the sum and the silane coupling agent of an acrylic polymer (B) (C) to [(A + B) / ( C)] is 70 / 30-80 / 20 Der Rukoto Characteristic hydrophilic coating. In the nonvolatile component of the main agent,
The content of the colloidal silica sol (A) is 10 to 30% by mass,
The acrylic polymer (B) content is 30-45% by mass,
The content ratio of the silane coupling agent (C) is 10 to 20% by mass,
The content ratio of the (D) polylactone polyol is 15 to 30% by mass,
The hydrophilic coating agent according to claim 5, wherein the content ratio of the surfactant (F) having active hydrogen is 0 to 15% by mass. The mass ratio [(A) / (B)] of the component (A) and the component (B) is 5/95 to 95/5,
The mass ratio [(A + B) / (C)] of the sum of the component (A) and the component (B) and the component (C) is 70/30 to 80/20 ,
The hydrophilic coating agent according to claim 5 or 6, wherein the mass ratio [(B) / (D)] of the component (B) and the component (D) is 90/10 to 10/90.   The hydrophilic coating agent according to any one of claims 5 to 7, wherein the acrylic polymer (B) has a hydroxyl value of 10 to 70.   The hydrophilic coating according to any one of claims 5 to 8, wherein the curing agent (E) contains at least one selected from the group consisting of a nurate polyurethane resin, a burette polyurethane resin, and an allophanate polyurethane resin. Agent.   The hydrophilic coating agent of any one of Claims 5-9 which further contains a hardening metal catalyst (G).   A hydrophilic film obtained by applying the hydrophilic coating agent according to any one of claims 1 to 4 to a substrate and curing it.   A hydrophilic film obtained by applying the hydrophilic coating agent according to any one of claims 5 to 10 to a substrate and curing it.   A hydrophilic substrate coated with the hydrophilic film according to claim 11.   A hydrophilic substrate coated with the hydrophilic film according to claim 12.